Summary: Multifunctional poly(tartar amides) have been synthesized and used as bio‐inspired antifreeze additives. It is shown that these polymers strongly interfere with the crystallization process of water in comparison to commercially available commodity polymers. While the addition of the poly(tartar amides) results in minor freezing point depression, as is shown by differential scanning calorimetry, a strong change in the ice crystal morphology is evident. Wide‐angle X‐ray scattering and optical microscopy indicate that the hexagonal structure of undisturbed ice‐crystals is oriented and partly deformed.
Light microscopy image of ice crystals at 223 K after a freezing assay with poly(tartar amides) shown at a polymer concentration of 2 wt.‐%. 相似文献
A glutathione peroxidase(GPX) mimic, 2-selenium bridged β-cyclodextrin(2-SeCD), was synthesized. In order to examine its role and mechanism in treating stroke we chose stroke-prone spontaneously hypertensive rats(SHRsp) as animal model. 56 SHRsps of 8-week olds were randomly divided into several groups: test groups (low, moderate, high dose of 2-SeCD) and control groups(positive and negative). After onset of the stroke, the rats in test groups were orally administrated with different amounts of 2-SeCD, the positive control group with ebselen, and the negative control group with drinking water. The treatment lasted two weeks, followed by observation of the rats for 10 days, meanwhile blood pressure, biochemical parameters of plasma, and the contents of nitric oxide(NO) and malondialdehyde(MDA) in plasma and brain were determined. The results show that there were significant differences in contents of NO and MDA in plasma and brain between the test groups(high, moderate dose of 2-SeCD) and negative control group. The NO contents of the test groups were obviously higher than that of the negative control group (P〈0.01). The MDA contents of the test groups(high, moderate dose of 2-SeCD) were obviously lower than that of the negative control group(P〈0.01). The mechanism of 2-SeCD in treating stroke was discussed, which maybe related to the increase of NO and the decrease of MDA in plasma and brain tissue, but the exact mechanism should be further studied. Moreover, the tendencies of changes in systolic blood pressure, contents of NO and MDA, and other physiological parameters for the test groups were shown to be much better than the corresponding parameters for the positive group(the group with ebselen)(P〈0.05), indicating that the treatment effect of 2-SeCD is better than that of ebselen. 相似文献
A new generation of glutathione peroxidase enzyme mimic based on organotellurium was introduced. The catalytic cycles of these mimics, tellura and tellenol, were clarified by density functional theory and solvent-assisted proton exchange procedure as an indirect proton exchange chain. From the kinetic viewpoint, the oxidation of tellura (ΔG≠ = 23.55 kcal mol−1) was considered as the rate-determining step using a single-step process. Various behaviors of tellenol were examined in the reduction of tellurenylsulfide based on methanethiol nucleophilicity. On the basis of the turnover frequency calculations, during the catalytic cycles of tellura and tellenol, the rate of the catalytic cycle of tellura is faster than that of tellenol. A decrease in the electron density and an increase in the Laplacian from the reactant to the transition states are evidence of the bond rupture, whereas an opposite change is evidence of the bond formation. Finally, different analyses of the electron location function and localized orbital locator within the quantum theory of atoms in molecules were applied and discussed. The covalent nature of the intramolecular interactions suggests that the Te⋯N interaction is stronger than that of Te⋯H. Finally, based on different analyses, tellura can be considered the more reactive GPx mimic than tellenol. 相似文献
Direct electrochemistry of catalase (Ct) has been studied on single wall carbon nanotubes (SWNTs) modified glassy carbon (GC) electrode. A pair of well-defined nearly reversible redox peaks is given at -0.48 V (vs. SCE) in 0.1 mol/L phosphate solution (pH 7.0).The peak current in cyclic voltammogram is proportional to the scan rate. The peak potential of catalase is shifted to more negative value when the pH increases. Catalase can adsorb on the SWNTs modified electrode. 相似文献
The voltammetric behavior of the superoxide dismutase/catalase mimics [(N,N′‐bis(salicylidene)ethylenediamine)Mn(III)]Cl (or salenMn(III) chloride) 1 and [(N,N′‐bis(3‐methoxysalicylidene)ethylenediamine)Mn(III)]Cl (or 3,3′‐methoxysalenMn(III) chloride) 2 in acetonitrile is described. Both compounds show quasi‐reversible one‐electron reductions to the Mn(II) compound. Electroanalytical techniques are used to follow the reaction between superoxide and 1 and 2 and it is shown that it is the reduced Mn(II) compounds which scavenge superoxide. It is also shown that both compounds electrocatalytically generate superoxide in the presence of dissolved dioxygen. The rate constant for this reaction was determined for both compounds using microelectrode steady state voltammetry. A general reaction scheme for interactions between these compounds and both dissolved dioxygen and superoxide is proposed. 相似文献
BACKGROUND: The formation of native disulfide bonds between cysteine residues often limits the rate and yield of protein folding. The enzyme protein disulfide isomerase (PDI) catalyzes the interchange of disulfide bonds in substrate proteins. The two -Cys-Gly-His-Cys- active sites of PDI provide a thiol that has a low pKa value and a disulfide bond of high reduction potential (Eo'). RESULTS: A synthetic small-molecule dithiol, (+/-)-trans-1,2-bis(2-mercaptoacetamido)cyclohexane (BMC), has a pKa value of 8.3 and an Eo' value of -0.24 V. These values are similar to those of the PDI active sites. BMC catalyzes the activation of scrambled ribonuclease A, an inactive enzyme with non-native disulfide bonds, and doubles the yield of active enzyme. A monothiol analog of BMC, N-methylmercaptoacetamide, is a less efficient catalyst than BMC. BMC in the growth medium of Saccharomyces cerevisiae cells increases by > threefold the heterologous secretion of Schizosaccharomyces pombe acid phosphatase, which has eight disulfide bonds. This effect is similar to that from the overproduction of PDI in the S. cerevisiae cells, indicating that BMC, like PDI, can catalyze protein folding in vivo. CONCLUSIONS: A small-molecule dithiol with a low thiol pKa value and high disulfide Eo' value can mimic PDI by catalyzing the formation of native disulfide bonds in proteins, both in vitro and in vivo. 相似文献
Antioxidants are one of the main ingredients that protect food attributes by preventing oxidation that occurs during processing, distribution and end preparation of food. Physiological antioxidant protection involves a variety of chemical system of endogenous and exogenous origin in a multiplicity of pathways. Associate to this, researches have been directed in the development of methods as biosensors that can characterize antioxidants capable of removing harmful radicals in living organisms in an adequate way. Biosensors have represented a broad area of technology useful for environmental, food monitoring, clinical applications and can represent a good alternative method to evaluate the antioxidant status.The demonstration of the highlighted current application of biosensor as a potential tool to evaluate the antioxidant status is the main aim of this review. 相似文献